Drastically oxidized water-insoluble oxyalkylated triricinolein and method of making same



Patented Nov. 16, 1943 DRASTICALLY OXIDIZED WATER-INSOLU- BLE OXYALKYLAT AND METHOD OF MAKING SAME Melvin De Groote, University City,

Webster Groves, Mo., assi Petrolite Corporation, Ltd., a corporation of Delaware Original application July 7, 1941,

Keiser,

No Drawing.

ED TRIRICINOLEIN and Bernhard gnors to Wilmingtom DeL,

Serial No. 401,383. Divided and this application November 4 C ai s.

This invention relates to a. new chemical compound or composition of matter and to the manufacture of same, our present application being a division of our co-pending application, Serial No. 401,383, filed July I, 1941, Patent No. 2,307,- 495.

One object of our invention is to provide a new chemical product or composition of matter, that is particularly adapted for use as a demulsifier for crude oil emulsions.

Another object is to provide a practicable method for manufacturing said new compound or composition of matter.

The new composition of-matterthat constitutes our'present invention, is obtained by blowing or oxidation of water-insoluble oxyalkylated triricinolein, particularly oxyalkylated castor oil, and more specifically, oxyethylated castor oil. The manner of blowing or oxidizing such products is substantially the same as is employed to oxidize or blow castor oil, ricinoleic acid, and the like. I

It is well known that oxidized oils can be obtained from castor oil, ricinoleic acid and various derivatives of ricinoleic acid, such as monoricin olein, diricinolein and polyricinoleic acids. They are produced by the common practice of blowing or oxidizing castor oil and similar fatty oils or acids, particularly non-drying, unsaturated fatty oils, by means of a gaseous medium, such as air, oxygen, ozone, or ozonized air. The gaseous medium, such as air, may be moist or dry and the oxidation may take place in the presence or absence of a catalyst. The catalyst may be or a metallic type, such as lead ricinoleate, cobalt ricinoleate, manganese ricinoleate, etc.; or it may be of the organic type which produces peroxide, such as alpha pinene, linseed oil, etc. Oxidation may take place at atmospheric pressure or superatmospheric pressure, 1. e., pressures up to or including 200 pounds gauge pressure, and at any temperature slightly above the boiling point of water, for instance, 120 C., up to any temperature which does not produce undue decomposition by pyrolytic reaction.

The time of blowing may be fairly brief, for example, 8-10 hours; or it may be quite extensive, for instance, as long as 10-12-44 days, the longer time periods being employed generally when the temperature is Just slightly above the boiling point of water, and when oxidation is with air at atmospheric pressure.

30, 1942, Serial No. 467,475

One method of preparing drastically-oxidized castor oil is described in U. 8. Patent No. 2,023,979, dated December 10, 1935, to Stehr.

Also see U diflferent from those obtained by Patent No. 2,183,487, dated December 12, 1939, to Colbeth.

Thus, the same conventional procedure or procedures employed for the oxidation or castor oil or similar compounds is equally suitable for the blowing or oxidation of water-insoluble oxyalkylated triricinoleins. In'most instances, the period of oxidation is apt to be much longer. For instance, it may require two or three times as long under similar conditions to blow or oxidize oxyalklated triricinoleins to the same degree of oxidation as is required for castor oil. Inversely, if one attempts to obtain the same degree of oxidation within the same period of time, the step of oxidation itself must be more vigorous.

It is well known that the exact composition of ordinary oxidized castor oil is not known. This has been a matter of comment from time to time in the literature, including the patent literature dealing with arts in which blown castor oil is contemplated. However, it is obvious that the nature of the products obtained by the oxidation of oxyalkylated triricinolein must be significantly the oxidation of castor oil. It is obvious that oxidized water-insoluble oxyalkylated triricinolein must be of a different nature than ordinary oxidized castor oil.

It is well known that if triricinolein, preferably in the form of castor oil, is treated with an oxyalkyl'ating agent, particularly ethylene oxide, propylene oxide, butylene oxide, glycidol, or the like, and if one employs a large molecular pro portion of the oxyalkylating agent for each mole of occurrence of the ricinoleyl radical, that one can convert castor oil into a water-soluble product. The conventional procedure is well known, and generally speaking, involves nothing more or less than heating castor oil in the presence of successive small amounts of alkylene oxide or the like, under comparatively low pressures and fairly low temperatures, and usually in the presence of an alkaline catalyst, as, for example, sodium ricinoleate. The temperatures employed are generally above C. and below 200 C. The pressures employed are generally above 100 pounds gauge and below 300 pounds gauge pressure. Sometimes oxyalkylation is conducted in a continuous manner by introduction of the ethylene oxide in a gaseous state. More frequently, and most conveniently, the oxide is introduced in a liquid form in a comparatively small amount, for instance, 300 pounds of castor oil and 30 pounds of ethylene oxide, along with approximately one pound of sodium ricinoleate. Reacis allowed to take place under pressure in the manner above described until all the ethylene oxide is absorbed. Another portion of ethylene oxide is added, and the procedure repeated until water solubility is obtained. Not infrequently as many as 30 pound moles of the oxyalkylating agent are employed for one pound mole of triricinolein, in order to obtain complete water solubility. Needless to say, ethylene oxide promotes solubility in lower molecular proportions than propylene oxide or butylene oxide. Furthermore, ethylene oxide is preferable, due to its greater reactivity.

We have found that if one oxyalkylates triricinolein with any of the oxyalkylating agents indicated, particularly ethylene oxide, to a point definitely short of water solubility, and if one employs such water-insoluble oxyalkylated triricinolein or triricinoleins instead of triricinolein in a conventional oxidation or blowing operation of the kindconventionally employed in connection with castor oil, one obtains a new composition of matter which is particularly efiective as a demulsifier for water-in-oil emulsions. Such material has utility in other arts, such as a break inducer in the doctor treatment of sour hydrocarbons, as a plasticizer in the manufacture of plastics, and as an ingredient in furniture polishes, etc.

In view of what has been said previously, it hardly appears necessary to give further directions as to the manufacture of the product herein contemplated as ,a new composition or matter, and particularly as a demulsifier for petroleum emulsions of the water-in-oil type. However, for purposes of convenience, the following is included:

oxyalkylated triricinolein, Example 1 One pound mole of triricinolein in the form of castor oil is treated with three pound moles of ethylene oxide in the manner previously described.

Oxyallcylated triricinolein, Example 2 The same procedure is'followed as in Oxyalkyl- :ated triricinolein, Example 1, preceding, except \that six moles of ethylene oxide are employed instead of three moles.

oxyalkylated triricinolein, Example 3 The same procedure is followed as in Oxyalkylated triricinolein, Example 1, preceding, except that nine moles of ethylene oxide are employed instead of three moles.

Composition of matter, Example 1 One thousand pounds of water-insoluble oxyalkylated triricinolein of the kind exemplified by Example 1, preceding, is placed in an oxidation vessel, so that the depth of reactant through which air is forced, is at least 3 feet, and steam coils are used soas to maintain a temperature of approximately to C. No catalyst is added. The incoming air is distributed through a connection with a suitable number of small openings. Air is passed through at a rate so as to obtain uniform distribution and complete contact with the mass to be oxidized. The material is oxidized for a period of time varying from 300 hours to 500 hours, but, in any event, oxidation is stopped at a point short of stringiness or incipient rubber-like character. Other conventional oxidation procedures of the kind employed in the oxidation of castor oil may be used, if desired.

Composition of matter, Example 2 The same procedure is followed as in Composition of matter, Example 1, preceding, except that one employs an oxyalkylated triricinolein of the kind exemplified by Example, 2, preceding, instead of the kind described under Example 1, preceding.

Composition of matter, Example 3 The same procedure is employed as in Composition of matter, Example 1, except that one employs an oxyalkylated triricinolein of the kind exemplified by Example 3, preceding, instead of the kind described under Example 1, preceding.

We have found that the particular chemical compounds or reagents herein employed as demulsifiers may also be used for other purposes, for instance, as a break inducer in doctor treatment of the kind intended to sweeten gasoline, as plasticizers in the manufacture of resins and plastics, and as an ingredient of furniture polish.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A new composition of matter, consisting of drastically-oxidized water-insoluble oxyalkylated member of the class consisting of triricinolein and castor oil.

2. A new composition of matter, consisting of drastically-oxidized water-insoluble oxyethylated member of the class consisting of triricinolein and castor oil.

3. A new composition of matter, consisting of a drastically-oxidized water-insoluble oxyethylated castor oil; the oxyethylation of said castor oil involving at least three and not more than nine'moles of ethylene oxide for each mole of triricinolein employed prior to oxidation.

4. In the manufacture of a composition of matter as. defined in claim 1, the step of oxyalkylating member of the class consisting of triricinolein and castor oil to a point short of water solubility and then subjecting such resultant to drastic oxidation by means of a gaseous oxygen-containing medium.

MELVIN DE GROOTE. BERNHARD KEISER. 

